Metal working lubricating compositions



United States Patent C) ll/IETAL WORKING LUBRICATING COMPOSITIONS Thomas E. Reamer, El Cerrito, Calif., assignor to Shell Development Company, Emeryville, Calif., a corporation of Delaware No Drawing. Application March 28, 1951, Serial No. 218,099

6 Claims. Cl. 25218) This invention relates to aqueous emulsions particularly suitable for use in numerous industrial metal-working processes such as metal drawing, rolling, stamping, forging, cutting, and the like. These lubricants are especially valuable for cold drawing of wire, rod, tubing and shapes.

Problems encountered in lubricating metals under conditions of the uses referred to above, are particularly complex because of the various factors encountered, such as high temperature, high pressure, presence of foreign bodies or contaminants, and the like. To effectively lubricate under these adverse conditions, the lubricant must act both as a lubricant and, in some cases, as a coolant.

In the field of metal drawing and rolling, conventional lubricants, therefore, such as palm oil, black oil or lubricating compositions containing soaps, graphite, lime and the like have serious drawbacks and difiiculties are encountered in their use in that these generally available lubricants are incapable of withstanding high pressures and at the same time providing satisfactory lubrication; this results in scoring and wear of the metal being worked. Die wear is also excessive. Additionally, various lubricants, such as oils and greases, have a tendency to stain metals and/or to cause metal pick-up, or are difiicult to apply to the metal surface being treated, and even more difficult to remove therefrom after being worked.

To meet the requirements demanded of a good metalfabricating lubricant of the above class, such lubricant must have as essential properties: high film strength, ability to reduce friction and prevent Welding, ability to wet the metal surface being worked and to adhere thereto, ability to produce a good surface finish, property of easy application and removal, and freedom of causing staining or discoloration; the lubricant must also have good stability and the property of causing fines, abrasives and the like to settle and separate out of the lubricating system.

It is an object of this invention to provide an improved metal-working lubricant which meets more satisfactorily the above requirements. It is another object of this invention to provide a lubricant for metal working which is stable and non-corrosive. Still another object of this invention is to provide a metal-working lubricant having the property of resisting displacement from metal surfaces. Furthermore, it is an object to provide a metalv.working lubricant which is non-staining and which can be easily applied and removed from lubricated surfaces. A more specific object is to provide an improved lubricant for use in the working of stainless steels.

It has now been discovered that an excellent metalworking lubricant can be provided by forming an aqueous emulsion containing as the active ingredients a viscous hydrocarbon having a viscosity in centistokes of at least 350 or 400 at 210 F., and preferably above 700 centistokes at 210 F., an emulsifier, preferably cationic in character, a metal reactive extreme pressure agent and a mineral filler, said active ingredients being dispersed in water in certain amounts as will be hereinafter fully set forth. An excellent metal-working lubricant of this 2,722,515 Patented Nov. 1, 1955 2 invention can be prepared by forming: (A) an organic mixture comprising (1) a heavy hydrocarbonaceous material of which a bitumen is preferred, (2) an emulsifier, preferably cationic, e. g., an amine salt and (3) an extreme pressure agent, preferably one capable of reacting with contacting metals being worked such as extreme pressure agents capable of releasing chlorine: said three active materials being so proportioned that the bitumen constitutes the major part of said mixture and the viscosity of the total mixture is between 500 and 2000 centistokes at 210 F. and preferably between 700 and 1000 centistokes at 210 F. and (B) a slurry comprising a mixture of water and a mineral filler: said mixtures of (A) and (B) being admixed in such proportions as to form a stable emulsifiable concentrate, preferably in the ratio of from 1:1 to 1:5 respectively, which concentrate can be used as the metal working lubricant or diluted with from 1 to 20 parts of Water and used as a lubricant.

GROUP A MIXTURE Viscous or heavy hydrocarbon materials The viscous or heavy hydrocarbon material having a viscosity in centistokes of at least 350 at 210 F. can be a natural viscous hydrocarbon such as viscous distillate or residue petroleum fraction, a bitumen (which is preferred) or a synthetic hydrocarbon such as olefinic polymers exemplified by polyisobutylene and the like, or mixtures thereof.

Bitumen, which is preferred in making up the mixture of Group A, can be an asphaltic bitumen obtained by various means during the refinement of crude oils. The asphaltic bitumen specifically may be obtained as a residue from crude oil during the distillation process, or it may be obtained from acid tars in the treatment of lubricating oils with sulfuric acid, or it may be obtained during the deasphaltizing treatment of lubricating oils bearing petroleum fractions with solvents or deasphalting agents.

The production of asphaltic bitumen by distillation of asphaltic base crude oil or topped crude may be carried out under atmospheric pressure or under reduced pressure. The distillation of the crude is continued until the residue in the still has the desired penetration. Thus a crude-oil heated to a temperature of 40 to 50 C. is fed into an evaporator where vapors are flashed off and the residue is stripped with the assistance of superheated steam at 280 to 300 C. The residue which is the asphaltic bitumen is drawn off from the evaporator through heat exchangers where it is cooled to 160 to 180 C. and thereafter stored.

Asphaltic bitumen can be removed from residual oils by the addition of low-boiling hydrocarbons which cause the precipitation of the asphaltic materials as a lower layer containing a small amount of the solvent. Thus an oil-containing asphaltic material can be dispersed in butane and heated under pressure. The mixture may then be treated with a solvent such as propane or ethane until the asphaltic material is precipitated. The quality of the asphaltic bitumen thus produced depends upon the nature of the residual oil, the solvent used, the proportion of solvent used, conditions of deasphalting, and other factors.

Asphaltic bitumens obtained by any of the above processes as well as by any other suitable means and source may be used as the base component of the coating composition of this invention. The preferred asphaltic bitumens are those which have softening points of between about and 250 F. and preferably between 100 and F. The asphalts may be blown if desired, by well known processes. Straight run asphalts are particularly desirable for use in compositions of this invention;

they are exemplified by materials having the properties shown in Table I.

Table I Spr. gr. at 77 F., rnin 1.024- Penetration at 77 F., 100 gr., 5 sec 21-30 Ductility at 77 F, crn., min 100 Flash point, Cleveland 0. C., F., min 590 Softening point R and B, F -c 128 Loss on heating at 163 C., 5 hrs., percent max..- 0.5 Pen. of residue, percent of Orig. min 80 Soluble in CS2, percent min 99.8 Soluble in CCl4, percent min 99.8 Ash, percent max 0.20

The asphalt generally comprises 80% to b of the Group A mixture. Part or all of the asphalt can be substituted with a hydrocarbon having a viscosity of at least 350 at 210 F. centistokes and preferably between 700-1500 at 210 F. centistokes, such as olcfinic polymers of high molecular weight, e. g., polybutenes, polyethylenes; copolymers of olefines and iso-olefins, copolymers of propyleneisobutylene, heavy residual mineral oils, viscous lube oil extracts, and the like.

acetate, Octadecylammonium acetate, octadecylammoniurn propionate, rosin ammonium butyrate: dodecyltrimethylammonium chloride, octadecyltrimethylam monium chloride, Octadecylammonium phosphate, cetyl- I dimethylethylammonium bromide, octadecyldimethylbenzylammonium chloride, stearamide of diethylene triamine, and the like. Preferred are the oil-soluble alkylamine salts of low molecular weight acids, e. g., octadecylammonium acetate or chloride, oleylarnmonium acetate, cctadecylammonium propiontate, hexadecylammonium butyrate, N-octadecylpiperidinium acetate, octadecylcyclohexylammonium acetate, Octadecylammonium naphthenate, Octadecylammonium petroleum sulfcnate, etc.

The emulsifiers can be added to compositions of this invention in from 0.5 to 15% by weight based on the final blend.

Extreme PIESSZH'C agent The extreme pressure agents must be selected from the class which are chemically reactive with metals being worked, thereby forming protective films thereon which resist rupture under extreme stresses and pressures. Compounds of this class include halohydrocarbon compounds, haloorgano phosphorus compounds, e. g., thiophosphates, phosphonates; suliurized hydrocarbons, sulfurized fats, sulfurized fatty acids, sulfurized esters and the like; phosphorus-halogen-containing organic compounds, phosphorus halogen sulfur containing compounds, and the like. Examples of compounds which are particularly applicable in compositions of this invention include dibutyl trichloromethanephosphonate, monobutyl trichlorornethanephosphonate, monoisopropyl trichloromethanephosphonate, di(2-ethylhexyl) amine salt or octadecylamine salt of monobutyl trichloromethane phosphonate or its amide derivative, trichloromethanephosphonic acid, monobutyl trichloromethanephosphinate, mononyl trichloromethanethiophosphonate, tri(chloroethyl)phosphite, tributyl phosphate, tributyl thiophosphate, tricyclohexyl thiophosphate, tri(chloroethyl) thio- 4. phosphite, tricresyl phosphate: chlorinated paraffin wax, Anglomol 85, Parapoid 16 andl6S, and the like. Of the extreme pressure agents, preferred are the haloorganophosphonates and derivatives there, such as monobutyl trichloromethanephosphonate, the di(2-ethylhexyl)ainine salt or the octadecylamine salt thereof and the amide derivatives of said phosphonate and the like.

The extreme pressure agent can be present in compositions of this invention in from 0.5% to 5% by weight.

illustrative effective compositions of Group A are as follows:

Percent I. Unblown asphalt 89 C18 amine salt of monobutyl trichlorornethanephosphonate l Octadecylammonium acetate 10 Unblown asphalt 85 C18 amine salt of monobutyl trichloromethane phosphonate 2 Hexadecylammonium acetate 13 III. Unblown asphalt C18 amine salt of the mixtures of:

Monobutyl trichloromethanephosphonate Dibutyl trichloromethanephos- 3 phonate Trichloromethanephosphonic acid Tetradecylamine acetate 17 IV. Blown asphalt 87 Chlorinated parafiin wax (40% cl) 5 Octadecylammonium acetate 8 V. Unblown asphalt 83 Parapoid l6 1 5 Octadecylammonium acetate 12 VI. Unblown asphalt 89 Octadecylarnine salt of monobutyl triehloromethanephosphonate 1 Octadecyltrirnethylamrnonium chloride 10 VII. Unblown asphalt 83 Chlorinated parafiin wax (40% Cl) S Octadecyltrimethylammonium chloride 12 VIII. Unblown asphalt 88 Octadecylamine salt of monobutyl trichloromethancphosphonate 2 Octadecylammonium acetate 10 IX. Polybutene (1500 cs./210 F. visc.) 88 Octadecylarnine salt of monobutyl trichloromethanephosphonate 8 Octadecylamine acetate 10 X. Dutrex (lubricating oil extract) 89 Octadecylamine salt of monobutyl trichloromethanephosphonate 1 Octadecylammonium acetate 8 XI. Blown asphalt 89 Sulfurized oleic acid l Octadecylammonium acetate 10 XII. Blown asphalt 89 C18 amine salt of monobutyl trichloromethanephosphonate 1 Octadecylammonium acetate 10 XIII. Unblown asphalt 89 Anglamol 3 1 Octadecylammonium acetate 10 XIV. Blown asphalt 89 Anglamol 85 3 1 Octadecylammonium acetate 10 1 Note Composition F.

Softening point, C 42.4 Sp. Gr. 20/4" C 1.072 Viscosity cs. at 210 F 292 (low) M01. Wt 444 3 Note Composition D.

GROUP B MIXTURE As stated previously, the mixture of Group B is a slurry of water and a lubricating mineral filler which, when Composition D:

admixed with compositions of Group A, forms the de- Unblown asphalt 35 sired concentrated lubricating composition of this inven- Anglamol 85 2 3.5 tion which can be used as such or diluted with substan- Lithopone 10 tial amounts of water and used as a metal working lubri- Octadecylammonium acetate 5 cant. Water 46.5

The fillers should be non-abrasive in character and in- Composition E: clude zinc oxide, zinc sulfate, zinc sulfide, barium sulfate, Unblown asphalt 3S talc, chalk, mica, colloidal clays, e. g., bentonites, kaolin, Chlorinated paraflin wax (40% Cl) 5 tungsten monoand di-sulfide, molybdenum monoand Ditert-butyl hydroquinone 2 di-sulfide, lead oxide, basic lead carbonate, silver sulfate Lithopone 10 and the like, as well as mixtures thereof. Preferred fillers octadecylammonium acetate 5 are chalk, lithopone, White lead and zinc oxide. Water 43 The amount of filler used can vary over a wide range Composition F: and depends primarily upon the conditions under which Unblown asphalt 35 lubricants of this invention are used. Generally the Parapoid 16 3.5 filler can be present in from 2 to 40% and preferably Lithopone 10 from 5 to 15% based on the final composition, that is, Hexadecylammonium acetate 5 after the mixtures of A and B are admixed. Under mild Water 46.5 metal working operation, the filler can be omitted, if 20 Composition G: desired. Polybutene (1500 cs./210 F. visc.) 35

If desired, the emulsifying agent can be added in the Di-2-ethylhexyl amine salt of monobutyl triwater phase (B) rather than in the Group A mixture and chloromethanephosphonate 1 the two phases admixed under conditions mentioned Lithopone 10 above to form the final composition. octadecylammonium acetate 5 Preferred B type mixtures are: slurry of lithopone in Water 46 water, zinx oxide in water, barium sulfate in water, ben- Composition H: tonite in water, or these slurrys containing the cationic Unblown asphalt 35 emulsifiers of Group A, e. g., octadecylammonium ace- Di-Z-ethylhexyl amine salt of monobutyl tritate. chloromethanephosphonate 1 The final compositions of this invention are prepared c OXide 10 by admixing mixtures of A with B in desired proportions Dodecyltrimethylammoflium Chloride 5 such as in the ratios of 1:1 or 1:5, preferably under agitat- 46 ing conditions, with or without the application of heat, Composltlon I: until a stable emulsion has formed. Unblown asphalt 38 Illustrative examples of final concentrate emulsions of Monobutyl tnchlfnomethanephosphonate"" 2 this invention which are particularly suitable for the drawgfiifig acetate mg of stainless steel are. Water 45 Composltlon A 1: Percent 40 1 Compositions A to I were prepared by combining suitable Unblown asphalt (Table I) 40 fg-" g :P 5 t a d C18 amine salt of monobutyl trichloromethprepa i'gd ii y Lubriid borg ratioii i ammb organic compoun anephosphonate 1 f fggig g gggg ggf figs fatty Organic mate- Octadecylammonrum acetate 5 Lithopone 30 In order to illustrate the outstanding lubricating prop- Water 24 erties whlch composltlons of this lnventlon possess they Composition B: were sub ected to the following test:

In actual plant operation, Type 304 stainless steel tubes Unblown asphalt (Table I) 38 having an initial outside diameter of 1 inches were re- Octadecylamme Salt of monobutyl tnchloro duced about 42% in cross-sectional area by cold drawm3thanfiphosphoDate 1 ing with Carboloy dies and mandrels with the aid of Llthopone 10 lubricants as identified in the table below and the supe- Octadecylamm nium a tat 5 riority of lubricants of this invention over the best known Water 46 available drawing lubricant can be clearly noted.

Cold drawing of stainless steel on a drawbench [Type 304, oxidized stainless steel tubing, ll- O. D.]

R e iic- D rawi'ng ohatfier Internal Total Die Mandrel Compositlon tion Pep Speed, During Mandrel Pickup Scoring force force force cent flL/mm. Draw of tube (Lb.) (Lb.) (Lb.)

B 42 9, 400 7, 700 1, 700 D-.. 42 9, 250 7, 300 1, 950 42 9, 000 7, 150 1,850 42 7,800 5,850 1,950 H 42 7,800 0, 100 1, 700 42 do do 9,000 0, 700 2,300 Graphi 42 18 Severe seglerree, Frac- Severe. 10,250 6,250 4,000 Bright Stock 42 Inches- Fractured.-- Severe. do 11,000

Composition C: Compositions of this invention can be applied to the Unblown asphalt 35 metal being worked by a suitable means such as brush- C18 amine salt of monobutyl trichloromething, dipping, spraying and the like, and the coated metal anephosphonate l stored until ready to be worked or directly drawn on Zinc oxide 10 application of the lubricant. octadecylammonium acetate 5 I claim as my invention: Water 49 1. A metal-working lubricating concentrate composi- 7 tion containing the following constituents in the following proportions:

' Percent by weight Unblown asphalt 35-38 Octadecylamine salt of monobutyl trichloromethanephosphonate 1 Lithopone 10 Octadecylammonium acetate 5 Water 4946 2. A metal working lubricating concentrate composition containing the following constituents in the following proportions:

Percent by weight Unblown asphalt 50 Gig amine salt of monobutyl trichloromethanephosphate 1 Octadecylammonium acetate 5 Lithopone 30 Water 24 nium acetate and octadecylammonium acetate; and (B) a water slurry containing from 2% to of a nonabrasive inorganic lubricating filler, the ratio of (A) to (B) ranging from 1:1 to 1:5, respectively.

5. A metal working lubricant concentrate containing: (A) from to of unblown asphalt, from 0.5% 5% of octadecylamine salt of monobutyl trichloromethanephosphonate and from 0.5% to 10% of octadecylammonium acetate, and (B) a water slurry containing from 2% to 40% of a non-abrasive inorganic lubricating filler, the ratio of (A) to (B) ranging from 1:1 to 1:5, respectively.

6. A metal working lubricant concentrate containing: (A) from 80% to 90% of unblown asphalt, from 0.5 t0 5% of octadecylamine salt of monobutyl trichloromethanephosphonate and from 0.5% to 10% of octadecylammonium acetate and (B) a water slurry containing from 5% to 15% of lithopone, the ratio of (A) to (B) ranging from 1:1 to 1:5, respectively.

References Cited in the file of this patent UNITED STATES PATENTS 1,440,356 Morrell June 22, 1920 1,952,973 Craig Mar. 27, 1934 2,256,877 Bertsch Sept. 23, 1941 2,466,647 Stern Apr. 5, 1949 2,552,913 Waugh May 15, 1951 OTHER REFERENCES Vol. 35, page 127, Industrial and Engineering Chemistry. 

1. A METAL-WORKING LUBRICATING CONCENTRATE COMPOSITION CONTAINING THE FOLLOWING CONSTITUENTS IN THE FOLLOWING PROPORTIONS: 